Fast drying coatings

ABSTRACT

Novel, rapidly drying, low volatile organic compound (VOC), minimal dot gain coatings, (including lithographic ink and varnish systems) are herein described. These systems dry sufficiently rapidly, that their usage eliminates ink drying speed as the rate limiting factor in most lithographic printing applications. In addition to providing enhanced drying rates as compared with their conventional counterparts, the rapid drying, low/no VOC lithographic coating systems of the instant invention can provide the user with significant improvement in dried film rub resistance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Application Ser. No. 60/408,916,filed Sep. 5, 2002, which is incorporated by reference in its entirety.

BACKGROUND

Conventionally, lithographic (litho) inks, and varnishes have beendesigned to dry via combination of solvent evaporation and oxidativepolymerization of unsaturated components.

Consequent to increasing concerns regarding the health, safety, andenvironmental impacts of volatile organic compounds, (VOCs); thecontribution of this component (the evaporation of solvent is presentlyresponsible for the major proportion of conventional litho inks' andvarnish's drying speeds) to drying rates is anticipated to shrink in thefuture, as increasingly stringent limitations are placed on the usage ofVOCs. Stacking of fresh prints in order to conserve space, which istypical during long runs, frequently limits the efficacy of solventevaporation as a drying mechanism. Additionally the incorporation ofsolvents in litho inks results in undesirable distortion (e.g.,capillary spread prior to drying) of applied ink droplets (dot gain),thus limiting print resolution. The extent of dot gain beyond thatconsequent to mechanical gain tends to be roughly proportional to thepercentage of VOCs employed, hence solvent incorporation into litho inkformulations often limits print quality.

The oxidative-polymerization component of the drying of present(commercially useful) litho inks almost invariably requires accelerationby toxic heavy metals such as cobalt and manganese, and is oftenkinetically limited by oxygen availability, especially when printing onessentially non-porous surfaces, and/or when fresh prints are stackedtightly, minimizing air access. A number of technologies have beendeveloped to overcome drying rate limitations of conventional lithoinks; these acceleration techniques include, the inclusion of variousenergy input systems, such as thermal energy (heatset, and infrareddrying), electron beam (EB), and ultraviolet (UV) radiation. The lattermethodology typically requires incorporation of substantial proportionsof a combination of expensive, and often-toxic photo initiators, andrelated auxiliaries, in addition to the expensive hardware, intensiveenergy consumption, and radiation exposure hazards, implicit in thegeneration of short wave length radiation used in both EB and IV basedcuring systems.

U.S. Pat. No. 5,552,467 teaches the usage of thermally activatedcombinations of chemical reducing agents, and organic (hydro)peroxides,one placed in the ink and the other contained in fountain solution as ameans of overcoming the oxidative-polymerization drying component ratelimitations of heat set lithographic inks. The patent discloses the useof two-part systems that inherently exclude usage in single fluid inks,and is limited further limited by the reactivity of the components,resulting in relatively short shelf life of solutions and/dispersions ofmany organic (hydro)peroxides, and of reducing agents in unsaturated oilbased vehicles, especially those containing carbon black an/or heavymetal based pigments, and in gum containing fountain solutionconcentrates. The specified technology has not been claimed to beeffective for use in systems which must dry at/or near ambienttemperatures.

U.S. Pat. No. 5,173,113 teaches the utility of hydrogen peroxide as afountain solution additive for the acceleration of drying oflithographic inks, by a factor of approximately twofold. Thiscombination, however, is used as a two-part system, thus inherentlyprecluding use in single fluid inks, and is also limited by the severeinstability of hydrogen peroxide in the presence of many variablevalence metals.

U.S. Pat. No. 5,156,674 teaches the utility of combinations of sodiumperborate (which rapidly hydrolyzes on contact with water to producehydrogen peroxide) and zirconium salts as lithographic fountain solutiondrying accelerators.

It has now been surprisingly found that incorporation of low to moderatepercentages of multifunctional 2, 5-bis (preferably unsaturated) fattyacid esters of 1,4-bis oxa-2,5-cyclohexadiene-2,5-diols,(meth)acrylates, allyl and/or vinyl ethers into otherwise conventionallithographic inks and varnishes (2 to about 30 weight percent), bothsignificantly enhances the drying rates of these inks and enhances theutility of low levels (10 to 5,000 parts-per million (ppm)) of peroxyacid salts, (cofactor reducing agents are not required) as replacementsfor the thermally activated organic (hydro)peroxide-reducing agentcombination(s) and/or hydrogen peroxide as fountain solution additivedrying accelerators previously disclosed.

SUMMARY

The invention relates to compositions, methods of making thecompositions, and methods of using the compositions for coatingapplications. The coatings are suitable as inks, varnishes, paints, andthe like. In one aspect the coatings are fast drying, relative toexisting technologies, and offer other advantages (e.g., print quality,color fastness, reduced or no VOC components, reduced or no toxicmetal-containing components) useful in print and coatings applications.

The compositions of the invention incorporate moderate percentages of acombination of multifunctional 2, 5-bis (preferably unsaturated) fattyacid esters of 1,4-bis oxa-2,5-cyclohexadiene-2,5-diols,(meth)acrylates, allyl and/or vinyl ethers in lithographic inks andvarnishes (2 to about 30 weight percent), including into otherwiseconventional lithographic inks, and related vehicles and varnishes.

In one aspect, the invention is a composition (and methods of usingthem) having one or more 2,5-bis fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, and any of one or more multifunctional(meth)acrylates, vinyl ethers, or a combination thereof, wherein theamount of (meth)acrylate is less than 10 weight percent, (e.g., about 1to 7 weight %, about 3 to5 weight %, less than any integer % between 1and 10%) of the total composition. The composition can be one having aminimum of about 2% and a maximum of about 30 weight percent of acombination of one or more 2,5-bis fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, and one or more of any ofmultifunctional (meth)acrylates, vinyl ethers, or a combination thereof.In another embodiment, the composition includes at least one(meth)acrylate.

In other aspects, the compositions (and methods) delineated herein canbe those: having one or more 2,5-bis unsaturated fatty acid ester of1,4-bis oxa-2,5-cyclohexadiene-2,5-diol; further having one or moreinorganic salts of a peracid; having from about 10 to about 5,000 partsper million (ppm) of an inorganic salt of a peracid. In other aspects,the compositions (and methods) delineated herein can further includepigments; can further have one or more additional ink vehicle components(e.g., solids, alkyds, polyesters or polyamides); can further includewater; or can have one or more compounds delineated in any of the tablesherein (e.g., Tables A-C or 1-4).

In another aspect, the invention relates to an ink having any of thecompositions delineated herein, including those having one or more2,5-bis fatty acid esters of 1,4-bis oxa-2,5-cyclohexadiene-2,5-diols,and one or more of any of multifunctional (meth)acrylates, vinyl ethers,or a combination thereof, wherein the amount of (meth)acrylate is lessthan 10 weight percent, (e.g., about 1 to 7 weight %, about 3 to 5weight %, less than any integer % between 1 and 10%) of the totalcomposition.

Another aspect of the invention is a method of printing including usingan ink having any of the compositions delineated herein, including thosehaving one or more 2,5-bis fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, and one or more of any ofmultifunctional (meth)acrylates, vinyl ethers, or a combination thereof,wherein the amount of (meth)acrylate is less than 10 weight percent,(e.g., about 1 to 7 weight %, about 3 to 5 weight %, less than anyinteger % between 1 and 10%) of the total composition. The method canfurther include applying the ink to a press; can be lithographic,letterpress, flexo, gravure, etc.

In another aspect, the invention is a method of printing including usingany of the compositions delineated herein, including those having one ormore 2,5-bis fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, and one or more of any ofmultifunctional (meth)acrylates, vinyl ethers, or a combination thereof,wherein the amount of (meth)acrylate is less than 10 weight percent,(e.g., about 1 to 7 weight %, about 3 to 5 weight %, less than anyinteger % between 1 and 10%) of the total composition, as an inkvehicle. The method can further include that wherein the ink vehicle ismixed with a fountain solution, or that wherein the fountain solutionfurther includes an organic (hydro)peroxide or an inorganic salt of aperacid. The method can further include contacting the composition orink vehicle delineated herein with a fountain solution immediately priorto use in printing or immediately prior to application to a printingpress. The method can further include contacting the composition or inkvehicle delineated herein with water (e.g., air, water source, othermoisture source) immediately prior to use in printing or immediatelyprior to application to a printing press.

Another aspect of the invention is a composition made by the process ofcombining one or more 2,5-bis fatty acid ester of a 1,4-bisoxa-2,5-cyclohexadiene-2,5-diol, and one or more of any ofmultifunctional (meth)acrylates, vinyl ethers, or a combination thereof,wherein the amount of (meth)acrylate is less than 10 weight percent ofthe total composition. The method can further include combining one ormore additional compounds delineated herein (e.g., an inorganic salt ofa peracid or an organic hydroperoxide).

In one aspect, the compositions are any of those delineated hereinwherein they have reduced levels (relative to conventional amounts,e.g., <1 weight %, 0.05 to 0.7 weight %, of metal), or are devoid of,toxic heavy metals (e.g., cobalt, manganese), including in elemental orsalt forms.

Preferred embodiments of the instant invention include those litho inkformulations which incorporate from about 2 to about 12 weight percentof 2, 5-bis (preferably unsaturated) fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, in addition to 2 to about 15 weightpercent of one or more essentially non-volatile multifunctional(meth)acrylates and/or vinyl ethers in combination with the free radicalsources described above. Examples of the new and novel bisoxa-cyclohexadiene diol bis esters, which conform to the generic FormulaA (below); examples of same are provided in Table B. Multifunctional(meth)acrylates and vinyl ethers useful in the practice of thisinvention are legion; however, for the sake of brevity, ten examples ofeach are cited in Table B, and C respectively. These examples areintended to be illustrative, and not delimit the scope of thisinvention.

The introduction of said multifunctional 2,5-bis (preferablyunsaturated) fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, (meth)acrylates and/or vinyl ethers as(optionally partial) solvent replacements, not only substantiallyenhances the drying acceleration effects of (organic(hydro)peroxide—reducing agent combinations, and/or fountain solutionhydrogen peroxide addition, taught by the prior art, but additionallyprovides significant aesthetic improvements relative to the prior art.These improvements include the minimization of dot gain, and of ghosting(penetration of porous substrates by ink via capillary wetting) and gasghosting, increased gloss potential, and enhanced pigment dispersionrates. The upgrades enabled via the application of the teachings of thisinvention permits the formulator to design reduced and/or solvent freelitho inks, superior to their conventional, (alkyd-polyester-resin)based solvent borne analogs. The use of inorganic peroxy salts, asopposed to that of either organic(hydro)peroxides, when employed inconjunction with either conventional or single fluid lithographic inks,either in the ink or fountain solution, has been found to minimizeformulation stability problems, since most inorganic peroxy salts haveminimal solubility in the oil based ink phase, and insufficientoxidation potential to significantly damage fountain solutions and orrelated concentrates, under normal use and/or storage conditions.

As a practical matter, this invention teaches the use of litho inksystems, which employ low to moderate proportions of multifunctional2,5-bis (preferably unsaturated) fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, (meth)acrylates, and/or vinyl etherspreferably in combination with catalytic proportions of peroxy acidsalts. These peroxy acid salts may, usefully, be incorporated into theink and/or into the fountain solution (when employed in wet platelithography), at levels of the order of about 10 to about 5,000 partsper million (ppm). When said accelerators are activated via readilyapplicable techniques, e.g. chemically, thermally, and or exposure toradiation, these nascent free radical sources decompose to free radicalswhich affect rapid polymerization based cure of the ink.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DETAILED DESCRIPTION

The compositions and methods of the invention relate to coatings, and inone aspect inks. Materials that are standard and conventional in the artare suitable for use in the compositions and methods herein.

Lithographic printing is the art or process of printing from a flatplate in which the desired image is achieved by construction of saidplate such that selective adhesion of the printing ink to plate occursin the desired image area(s), followed by contact transfer of said imageeither directly, or indirectly to a substrate (e.g., paper, plastic,metal).

Unsaturated fatty acids are defined as materials having the compositestructure HOC(O)(CR¹R²)_(n)(R³C═CR⁴)m R₇ wherein m is an integer fromone to about 5, wherein n is an integer from 3 to about 20, and whereineach of the various R groups (e.g., R¹, R², R³, R⁴) is independentlychosen from among hydrogen or is a monovalent hydrocarbyl group havingfrom one to about four carbon atoms. The various (CR¹R²) and (R³C═CR⁴)need not be consecutive or in conjugation, but may be connected to eachother in any order. Unsaturated fatty acids useful in the compositionsand methods herein include, for example, those listed in the tablesherein.

(Meth)acrylate esters are herein defined as materials having the generalstructure [RCH₂═CRC(O)O]nR′, wherein n is an integer larger than 1; eachR is independently chosen from hydrogen, or a CH₃ group, and R′ ischosen from among hydrocarbyl groups having from two to about 20 carbonatoms each, except that the number of carbon atoms in each R′ must equalor exceed n. (Meth)acrylate esters useful in the compositions andmethods herein include, for example, those listed in the tables herein.

Inorganic salts of peracids (or peroxy acids) are herein defined assalts of acids containing the structure (O—O⁻), in which the cation hasa positive electrical charge on an atom other than hydrogen, or carbon.Inorganic salts of peracids useful in the compositions and methodsherein include, for example, those listed in the tables herein. In someaspects of the invention, the inorganic salts of peracids are used incatalytic amounts (e.g., less than about 0.5 weight percent, less thanabout 0.25 weight percent, less than about 0. 1 weight percent, based ontotal weight of the composition).

Organic hydroperoxides are defined as an organic compound containing thestructure C—O—O(R) wherein R is a chosen from among hydrogen, or a groupbonded through carbon to the peroxide oxygen. Organic hydroperoxidesuseful in the compositions and methods herein include, for example,those listed in the tables herein.

Multifunctional vinyl ethers are herein defined as organic chemicalswhich contain the structure [RRC═CRO]nR′ wherein n is a n integer largerthan 1; each R is independently chosen from hydrogen, or a CH₃ group,and R′ is chosen from among hydrocarbyl groups having from two to about10 carbon atoms.

A fountain solution is herein defined as an aqueous solution thatmaintains the hydrophyllic oleo phobic balance of the non-image to theimage area on a planographic plate as well as maintaining a protectivefilm to prevent oxidation of the non-image areas.

Pigments are a colored particulate which is essentially insoluble in itsvehicle. Pigments can be in any of a variety of colors and areexemplified by those delineated in the examples herein.

Dot gain is herein defined as the expansion of the image (sub)componentsafter application of same to the print substrate. This decreases detailclarity, and thus minimal dot gain is typically more desirable forhigher clarity images.

The variety of 2,5-bis (preferably unsaturated) fatty acid esters of1,4-bis oxa-2,5-cyclohexadiene-2,5-diols, (meth)acrylate esters, andvinyl or allyl ethers, useful in the practice of this invention is verylarge, however for the sake of brevity, only 10 examples of preferredmembers of each class of materials are provided in Tables A through C.The examples provided hereinafter are intended to be illustrative of,and not to exhaustive of nor to limit the scope of this invention. Thoseskilled in the art will easily be able to provide many more examples ofeach class of such components with minimal difficulty, and withoutdeparting from the teachings of this invention.

An ink vehicle is a combination of components that are suitable for inkcompositions. In one aspect, the ink vehicle contains certain componentsthat are incompatible for storage with other ink components (i.e., whenin contact, an irreversible reaction takes place, which may beundesirable or may be desired to be controlled such that the reactiontakes place immediately prior to, or concurrent with, use of theresulting product (e.g., ink) for printing). In such instance, one ofthe incompatible components is placed in the ink vehicle and the otheris placed in a second ink vehicle (e.g., fountain solution) for mixingimmediately prior to, or concurrent with, use. The ink vehicle caninclude any of the materials delineated herein, or can also include anystandard ink vehicle component know in the art, including for example,solids, alkyds, polyesters or polyamides suitable for ink or printingcompositions, and the like. The same material can be considered avarnish or coating when pigments are absent from the composition.Varnishes are expressly considered one aspect of the compositionsdelineated herein.

The compositions herein are useful in lithographic printingapplications. Such applications can be intaglio or off-set, includingsheet-fed, cold-web, and heat set web printing. The teachings of thisinvention are beneficial and applicable in the practice of letterpress,sheetfed, heatset and coldset forms of lithography; providing in eachinstance the opportunity to achieve faster production of improvedproducts.

The number and variety of nascent free radical sources, useful in thepractice of this invention is very large, however for the sake ofbrevity, only 10 examples of sources are provided, cf. Table A. Thosenascent peracid salts useful in conjunction with a specific lithographicprinting press configuration may be selected, in part, by the means ofactivation available. For example the absence of a radiant energy sourcewould preclude the utility of a radiation-activated system, and/or theuse of single fluid, dry plate lithography would preclude theapplicability of water and/or chemically activated systems.

Other embodiments of the invention include those specifically delineatedin the tables and examples herein. The examples provided hereinafter areintended to be illustrative of, and not to limit the scope of thisinvention

EXAMPLES

TABLE A Incorporated into Ink Material (I) or Fountain Preferredactivation Designation Peroxy acid salt Solution (F) methodology AAsodium peroxy I or F water. diphosphate AB sodium perborate I or F waterAC sodium persulfate I or F thermal, AD sodium peroxy I or F thermal,disulfate AE calcium perphthalate I or F thermal, or radiation AFAluminum I or F Water, or thermal. percarbonate AG Potassium perhenate IThermal, radiation, AI Potassium I thermal, or radiation permanganate AImagnesium per t- I water butoxide AJ sodium peracetate I or F thermal,radiation

Wherein R and R′, are each independently chosen from among 3 to 30carbon saturated or unsaturated monovalent hydrocarbyl or oxyhydrocarbylligands. R¹ and R² are each independently chosen from among hydrogen,and one to seven carbon saturated, aromatic or unsaturated monovalenthydrocarbyl ligands. TABLE B Material designation 1,4 bis oxacyclohexadiene-2,5-bis ester BA 3,6-bis methyl, bis linolenate BB2-butenoate, ricinoleate BC 3-(2-butenyl) bis 6,8-undecadienoate BDArachidonate, myristoleate BE n-octanoate, 2-propenoate BF 3,6-bisphenyl, crotonate, laurate BG 3-methyl-6-hexyl, bis isovalerate, BHPelargonate, versalate BI 3,6-bis methyl, bis tung oil fatty ester. BJ3-t-butyl,, 2-behenolate, 6-(2-methyl)-2-propenolate

TABLE C CA Multifunctional (meth)acrylates/vinyl ethers CB sorbitantetra methacrylate CC Tris allyl trimelitate CD tetrakis methylolacetone bis acrylate, undecanoate CE 2,3,2′,3′-tetrakis acrylato bispropyl ether CF Tris methylol propane tris methacrylate CG1,2,4-cyclohexane tris acrylate CH 2,5-furfuryl bis acrylate CI Bispentaerythritol tetrakis vinyl ether (mixed isomers) CJ n-hexanol1,2-tris vinyl ether

Example 1 Method for the preparation of 1,4-bis oxa-2,5-cyclohexadienebis esters(bis vinyl esters)

One mole of 2,5-bis oxo-1,4dioxane, was dissolved in 2 liters oftrimethyl cyclohexane, 0.5 grams of tetra isopropyl titanate was addedand the resulting solution heated to, well stirred, and maintained at1160±5° C. under nitrogen sparge, during the addition, over a four hourperiod of 2 moles of methyl linoleate, and for an additional three hoursthereafter. 1.92 moles of methanol (identity confirmed via gaschromatography) were collected, via distillation, during the heatingperiod. Analysis of the resulting product by high pressure liquidchromatography (HLPC)-mass spectroscopy (MS), and Fourier transforminfra-red spectroscopy (FTIR), indicated that 98 percent of the dioxaneand that 96 of the methyl linoleate had been consumed respectively toproduce a 91 mole % yield of the desired bis ester (R1 and R2 each ═H, Rand R′ each ═C₁₇H₂₉). Similarly prepared were a variety of analogs.Those analogs in which the two acyl ligands were dissimilar wereproduced via sequential addition of the acyl components, with a two hourequilibration period between acyl component type additions Therespective yields of the named product(s) (Isolated by preparative HLPC,and identified by MS and FTIR) are documented in Table 1. TABLE 11,4-bis oxa- Major cyclohexane-2,5- Yield product dione Acylate 1Acylate 2 Mole % BA 3,6-bis methyl isopropyl linolenate same 94 BBmethyl ethyl 37^(a) iso octadieneoate ricinoleate BC 3-(2-butenyl)methyl 6,8- same 89 undecadieneoate BD 3-methyl isopropyl methyl 42^(a)arachidonate mysteroleate BE methyl octanoate t-butyl 2- 44^(a)propenoate BF 3,6-bis phenyl methyl crotonate ethyl laurate 47^(a) BG2-methyl-5-hexyl ethyl isovalerate same 81 BH methyl pelagonate versalicacid 87 BI 3,6-bis methyl tung oil fatty acid, same 83^(b) BJ 3-t-butyl,isopropyl 2-methyl- behenolinic 52^(a) 2-propenoate acidNotes:^(a)mixed acylate bis ester, total bis acylate yield >75%.^(b)total (mixed) fatty acylate bis esters.

Example 2 Incorporation of Minor Proportions of Multifunctional(meth)acrylates and or Vinyl and/or Allyl Ethers, as (Partial/CompleteSolvent Replacements in Dual Fluid Lithographic Sheetfed Inks

Blue sheet fed litho inks were prepared by mechanically admixing andthree roll milling (to a Hegman grind of 7+) 345 g of Halite, 295 g of3010 (Lawter Chemical Co., tung-linseed oil based gloss varnishes), 160g of phthalocyanine blue pigment (No. Ciba Specialty Chemical Co.), 150g of conventional diluent, or VOC free reactive diluent(s) replacement,as specified in Table 2, 6 g of polytetrafluoro ethylene powder (MicroPowders-Fluoro 60), 2 g each of 12% cobalt, and 12% manganesenaphthenates. Optionally accelerator, as specified, was added to theindicated fluid. Ink tack was adjusted to 11 at 800 RPM, via theaddition of 40 g of a combination of Exxate 200, diluent as specified,and/or 3020 (Lawter Chemical Co. tung-linseed oil based gloss varnish).

The resulting inks were each separately evaluated by printing, using a300 line screen at normal density of 120 on an Xrite densitometer, on achrome coated 35 kg. paper stock, using a Komori 300×450 mm sheetfedpress, @9,000 impressions per hour, using Vam Corp.'s Total (fountainsolution concentrate) @80 g. per liter, and the minimal proportion ofisopropanol, as a fountain additive, required to eliminate scumming. Theresulting prints were each evaluated for drying rates, dot gain. Printyield (mileage), minimum fountain solvent requirements, maximum stackheight prior to visible offset and VOC values Were also determined, anddocumented in Table 2. TABLE 2 Minimum % Total Through Accelerator-fountain VOC Mileage % Max. Dry ppm/ alcohol g/kg 10³ m²/g Dot StackTime ID Diluent(s)-% I or F req. ink ink Gain Cm hour 2A Exxate none 8.5188 0.76 26 42 21 200-15 2B Exxate AA-5000/I 8.5 188 0.73 24 42 16200-15 2C BA-10 none none 7 1.06 5 60 13 2D BA-10 AA-500/I none 7 1.043.5 65 9 2E BE-7 none none 6 1.02 5.5 55 15 2E BE-7 H₂O₂- none 6 1.015.5 55 18 1,000/F 2F BE-7 AB-80/I none 6 1.02 5.5 55 15 2G BI-3, AD-none 3 1.11 4.9 75 6 CB-7 1,250/F 2H CD-9 none 2 25 0.98 7.8 55 13 2ICH-12 AF-15/I 1 14 0.96 8.2 60 10 2J Exxate AA-5000/I 3.2 75 0.86 14 4813 200-7 BB-4

Benefits demonstrated include: reduced dot gain, faster drying,reduced/virtual elimination of VOCs, enhanced print stacking tolerance.

Example 3 Incorporation of Minor Proportions of Multifunctional(meth)acrylates and or Vinyl and/or Allyl Ethers, as Partial/CompleteSolvent Replacements in Single Fluid Lithographic Cold Web (SubstrateMoisture-Humidity Activated) Inks

Black, single fluid, cold web litho inks were prepared by mechanicallydispersing and filtering ((through a 5 micron filter) 400 g of Ultrex110, 300 g of Nylin 5 (Lawter Chemical Co., tung-linseed oil based glossink vehicles), 140 g of black pigment (No. R400R Cabot Corp.), 7 g ofreflex blue pigment (BASF) 105 g of conventional diluent, or VOC freereactive diluent(s) replacement, as specified in Table 3, 4 g ofpolyethylene wax paste (No. Shamrock Industries), and 3 g ofpolytetrafluoro ethylene powder (Micro Powders-Fluoro 60). Optionallyaccelerator, as specified, was added to the ink. Tack was adjusted to 8at 800 RPM, via the addition of 40 g of a combination of diglyme,diluent as specified, and/or 3020 (Lawter Chemical Co. tung-linseed oilbased gloss varnish).

The resulting inks were each separately evaluated by printing, using a200-line screen at standard densities, on a calendared, uncoated 25 kg.paper stock, employing a Goss, 1 meter web press, using Toyo siliconeplates press, at maximum (drying rate, or press capability productionrates—19,000 impressions/hr.) The resulting prints were each evaluatedfor drying rates, dot gain. Print yield (mileage), requirements, minimumcompression (psi) necessary to effect visually detectable offset, andVOC values were also determined, and documented in Table 3. Substrateand printing local were both maintained at 22° C. and 60% relativehumidity, during printing. TABLE 3 Total Max. Max Accel- VOC Mileage %Comp. print erator- g/kg 10³ m²/g Dot Psi × rate ID Diluent(s)-% ppm inkink Gain 100 K 3A Propylene none 232 0.59 31 0.65 12.7 glycol-22 3BPropylene AE-1,000 234 0.61 27 0.95 14.9 glycol-22 3C Butyl none 2570.53 25 0.73 13.7 triglycol-25 3D Butoxy AF-250 262 0.54 23 0.80 15.4triglycol-25 3F BF-9, none 9 0.89 7 1.2 18.7 CF-11 3G BF-6, AE-500 90.89 8 >2.5 >19 CF-11 3H BG-19 AI-70 10 0.87 6 >2.5 >19 3I CH-22 AG-40 70.79 8 1.8 18.6 3J BC-17 AA-600 5 0.91 7 >2.5 >19

Benefits demonstrated include: reduced dot gain, faster drying (enablinghigher print rates), reduced/virtual elimination of VOCs, enhanced printpressure tolerance.

Example 4 Incorporation of Minor Proportions of Multifunctional(meth)acrylates and or Vinyl and/or Allyl Ethers, as (Partial/CompleteSolvent Replacements in Lithographic Heatset Web Inks

Yellow, red, cyan and black, litho heatset inks were prepared bymechanically dispersing and filtering (through a 5 micron filter) 400 gof A-1407, 300 g of Ultrex 110 (Lawter Chemical Co., tung-linseed oilbased gloss ink vehicles), 140 g of pigment 250 g of conventionaldiluent, or VOC free reactive diluent(s) replacement, as specified inTable 3, 4 g of polyethylene wax paste (No. Shamrock Industries), 20 gof Aluminum carbonate, and 3 g of polytetrafluoro ethylene powder (MicroPowders-Fluoro 60). Optionally accelerator, as specified, was added tothe ink. Tack was adjusted to 8 at 800 RPM, via the addition of 40 g ofa combination of Exxate 200, diluent as specified, and/or 3020 (LawterChemical Co. tung-linseed oil based gloss varnish).

The resulting inks were each collectively evaluated by two-sided fourcolor printing, using a 200-line screen at standard densities, on acoated 25 kg. paper stock, employing a Goss 1 meter web heatset press,conventional plates, a fountain solution containing 20 g/1 of Lithofontfountain solution cone (2-3%), and the minimum of IPA required toprevent scumming; and a 9 meter 160° C. oven equipped with a 5° C. chillroll, at maximum (drying rate, or press capability limited productionrates—22,000 impressions/hr.) The resulting prints were each evaluatedfor drying rates, dot gain. Print yield (average color mileage), minimumcompression (psi) necessary to effect visually detectable offset, andVOC Values were also determined. These are documented in Table 4. TABLE4 Total Average Max. Max Accel- VOC Mileage % Comp. print erator- g/kg10³ m²/g Dot Psi × rate ID Diluent(s)-% ppm ink ink Gain 100 K 4A Exxatenone 282 0.79 31 1.65 17.7 200-25 4B Exxate AE-1,000 284 0.81 27 1.9318.9 200-25 4C Exxate t-butyl 297 0.77 30 1.65 18.1 200-25 perox-ide-1,000 4D Methyl AF-250 185 0.74 24 0.80 18.4 linoleate-25 4F BF-9,none 9 0.86 6 2.2 21.7 CF-11 4G BJ-6, AE-500 9 0.88 8 >2.5 >22 CC-11 4HBG-19 AI-70 10 0.91 5 >2.5 >22 4I CI-22 AG-40 7 0.89 9 1.8 20.6 4J BC-17AA-600 5 0.92 8 >2.5 >22

Benefits demonstrated include: reduced dot gain, faster drying (enablinghigher print rates), reduced/virtual elimination of VOCs, enhanced printstacking tolerance.

The compounds of this invention (including as used in compositionsherein) may contain one or more asymmetric centers and thus occur asracemates and racemic mixtures, single enantiomers, individualdiastereomers and diastereomeric mixtures. E-, Z- and cis- trans-doublebond isomers are envisioned as well. All such isomeric forms of thesecompounds are expressly included in the present invention. The compoundsof this invention may also be represented in multiple tautomeric forms,in such instances, the invention expressly includes all tautomeric formsof the compounds described herein. All such isomeric forms of suchcompounds are expressly included in the present invention. All crystalforms of the compounds described herein are expressly included in thepresent invention.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, suitable methods andmaterials are described below. In case of conflict, the presentspecification, including definitions, will control. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting.

All references cited herein, whether in print, electronic, computerreadable storage media or other form, are expressly incorporated byreference in their entirety, including but not limited to, abstracts,articles, journals, publications, texts, treatises, internet web sites,databases, patents, and patent publications.

A number of embodiments of the invention have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention.Accordingly, other embodiments are within the scope of the followingclaims.

1. A composition comprising 2,5-bis fatty acid esters of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diols, and any of multifunctional(meth)acrylates, and vinyl ethers, or a combination thereof, wherein theamount of (meth)acrylate is less than 10 weight percent of the totalcomposition.
 2. The composition of claim 1 comprising a minimum of about2% and a maximum of about 30 weight percent of a combination of 2,5-bisfatty acid esters of 1,4-bis oxa-2,5-cyclohexadiene-2,5-diols, and anyof multifunctional (meth)acrylates, vinyl ethers, or a combinationthereof.
 3. The composition of claim 1, comprising a 2,5-bis unsaturatedfatty acid ester of 1,4-bis oxa-2,5-cyclohexadiene-2,5-diol.
 4. Thecomposition of claim 1, further comprising an inorganic salt of aperacid.
 5. The composition of claim 4, comprising from about 10 toabout 5,000 parts per million (ppm) of an inorganic salt of a peracid.6. The composition of claim 3, comprising from about 10 to about 5,000parts per million (ppm) of an inorganic salt of a peracid.
 7. An inkcomprising the composition of claim
 1. 8. The ink of claim 7, furthercomprising pigments.
 9. A method of printing comprising using an ink ofclaim
 7. 10. The method of claim 9, wherein the printing comprisesapplying the ink to a press.
 11. The method of claim 9, wherein theprinting is lithographic printing.
 12. The method of claim 9, whereinthe printing comprises printing on paper.
 13. A method of printingcomprising using the composition of claim 7 as an ink vehicle.
 14. Themethod of claim 13, wherein the ink vehicle is mixed with, a fountainsolution.
 15. The method of claim 13, wherein the fountain solutionfurther comprises an organic (hydro)peroxide and/or an inorganic salt ofa peracid.
 16. The composition of claim 1, further comprising one ormore additional ink vehicle components.
 17. The composition of claim 16,wherein the additional ink vehicle components are solids, alkyds,polyesters or polyamides.
 18. The composition of claim 1, wherein the2,5-bis unsaturated fatty acid ester of 1,4-bisoxa-2,5-cyclohexadiene-2,5-diol is a compound that is 3,6-bis methyl,bis linoleate; 2-butenoate, ricinoleate; 3-(2-butenyl) bis6,8-undecadienoate; Arachidonate, myristoleate; n-octanoate,2-propenoate; 3,6-bis phenyl, crotonate, laurate; 3-methyl-6-hexyl, bisisovalerate; Pelargonate, versalate; 3,6-bis methyl, bis tung oil fattyester; or 3-t-butyl, 2-behenolate, 6-(2-methyl)-2-propenolate.
 19. Acomposition made by the process of combining a 2,5-bis fatty acid esterof a 1,4-bis oxa-2,5-cyclohexadiene-2,5-diol, and any of multifunctional(meth)acrylates, vinyl ethers, or a combination thereof, wherein theamount of (meth)acrylate is less than 10 weight percent of the totalcomposition.
 20. The composition of claim 19, further comprisingcombining an inorganic salt of a peracid or an organic hydroperoxide.